Method of and apparatus for substrate pre-treatment

ABSTRACT

The present invention relates generally to a method and apparatus for converting a precursor material, preferably organometallic, to a film, preferably metal-containing, that is adherent to at least a portion of a substrate. Both method and apparatus include a pre-conversion step or section, and a step or section for substantial conversion of a portion of material from the pre-conversion step or section into the form of a predetermined pattern, wherein this substantial conversion results in a metal-containing patterned layer on the substrate.

FIELD OF THE INVENTION

[0001] The present invention relates generally to an apparatus and amethod for patterning a precursor via a pre-conversion step.

BACKGROUND OF THE INVENTION

[0002] The semiconductor and packaging industries, among others, utilizeprocesses to form thin metal and metal oxide films in their products.Conventional processes for forming metal and metal oxide films involvecostly equipment and are time consuming. Examples of such processesinclude evaporation, sputter deposition, thermal oxidation and chemicalvapor deposition. Evaporation is a process whereby a material to bedeposited is heated near the substrate on which deposition is desired.Normally conducted under vacuum conditions, the material to be depositedvolatilizes and subsequently condenses on the substrate, resulting in ablanket, or unpatterned, film of the desired material on the substrate.This method has several disadvantages, including the requirement to heatthe desired film material to high temperatures and the need for highvacuum conditions. Unless a screen or shadow is employed duringevaporation, an unpatterned, blanket film results from this process.

[0003] Sputtering is a technique similar to evaporation, in which theprocess of transferring the material for deposition into the vapor phaseis assisted by bombarding that material with incident atoms ofsufficient kinetic energy such that particles of the material aredislodged into the vapor phase and subsequently condense onto thesubstrate. Sputtering suffers from the same disadvantages as evaporationand, additionally, requires equipment and consumables capable ofgenerating incident particles of sufficient kinetic energy to dislodgeparticles of the deposition material.

[0004] CVD is similar to evaporation and sputtering but further requiresthat the particles being deposited onto the substrate undergo a chemicalreaction during the deposition process in order to form a film on thesubstrate. While the requirement for a chemical reaction distinguishesCVD from evaporation and sputtering, the CVD method still demands theuse of sophisticated equipment and extreme conditions of temperature andpressure during film deposition.

[0005] Thermal oxidation also employs extreme conditions of temperatureand an oxygen atmosphere. In this technique, a blanket layer of anoxidized film on a substrate is produced by oxidizing an unoxidizedlayer which had previously been deposited on the substrate.

[0006] Several existing film deposition methods may be undertaken underconditions of ambient temperature and pressure, including sol-gel andother spin-on methods. In these methods, a solution containing precursorparticles that may be subsequently converted to the desired filmcomposition is applied to the substrate. The application of thissolution may be accomplished through spin-coating or spin-casting, wherethe substrate is rotated around an axis while the solution is droppedonto the middle of the substrate. After such application, the coatedsubstrate is subjected to high temperatures which convert the precursorfilm into a film of the desired material. Thus, these methods do notallow for direct imaging to form patterns of the amorphous film.Instead, they result in blanket, unpatterned films of the desiredmaterial. These methods have less stringent equipment requirements thanthe vapor-phase methods, but still require the application of extremetemperatures to effect conversion of the deposited film to the desiredmaterial.

[0007] In one method of patterning blanket films, the blanket film iscoated (conventionally by spin coating or other solution-based coatingmethod; or by application of a photosensitive dry film) with aphotosensitive coating. This photosensitive layer is selectively exposedto light of a specific wavelength through a mask. The remaining materialmay also then be used as a pattern transfer medium, or mask, to anetching medium that patterns the film of the desired material or as acircuit or dielectric layer. If used as a mask or etching, then thisetch step, the remaining (formerly photosensitive) material is removed,and any by-products generated during the etching process are cleanedaway if necessary.

[0008] In another method of forming patterned films on a substrate, aphotosensitive material may be patterned as described above. Followingpatterning, a conformal blanket of the desired material may be depositedon top of the patterned (formerly photosensitive) material, and then thesubstrate with the patterned material and the blanket film of thedesired material may be exposed to a treatment that attacks the formerlyphotosensitive material. This treatment removes the remaining formerlyphotosensitive material and with it portions of the blanket film ofdesired material on top. In this fashion a patterned film of the desiredmaterial results; no etching step is necessary in this “liftoff”process. It is also known that the “liftoff” method has severelimitations with regard to the resolution (minimum size) that may bedetermined by the pattern of the desired material.

[0009] In yet another method of forming patterned films, a blanket filmof desired material may be deposited, e.g., by one of the methodsdescribed above, onto a substrate that has previously been patterned,e.g., by an etching process such as the one described previously. Theblanket film is deposited in such a way that its thickness fills in andcompletely covers the existing pattern in the substrate. A portion ofthe blanket film is then isotropically removed until the remainingdesired material and the top of the previously patterned substrate sitat the same height. Thus, the desired material exists in a patternembedded in the previously patterned substrate. The isotropic removal ofthe desired material may be accomplished via an etching process;commonly in the case of the formation of semiconductor devices it isenvisioned that this removal is effected through a process known aschemical mechanical planarization (“CMP”). This involves the use of aslurry of particles in conjunction with a chemical agent to removesubstantial quantities of the desired material through a combination ofchemical and mechanical action, leaving behind the desired material inthe desired places embedded in the patterned substrate.

[0010] While some of these methods are more equipment-intensive thanothers and differ in the use of either solution- or vapor-phase methods,such conventional processes for forming metal and metal oxide films isnot optimal because, for example, they each require costly equipment,are time consuming, require the use of high temperatures to achieve thedesired result, and result in blanket, unpatterned films where, ifpatterning is needed, further patterning steps are required. Many ofthese methods suffer the additional disadvantage of, in many cases,forming polycrystalline films which may not be suitable for a variety ofapplications. A desirable alternative to these methods would be the useof a precursor material that may be applied to a substrate andselectively imaged and patterned to form an amorphous film without theneed for undesirable intermediate steps.

[0011] One use of thin films in semiconductor processing is for theformation of thin top-surface imaging (hereafter “TSI”) layers,typically atop organic layers that have already been applied to thesubstrate. In this instance, the organic layer need not be photoactive,since the thin film to be deposited will be subsequently patterned usingconventional methods. The use of these thin films for TSI confersseveral process advantages, including resistance to plasma etching notafforded by the use of photoresist masks, and the increased resolutionof the lithographic process afforded by a very thin film. Typical thinfilms for TSI include metal and silicon nitride and oxide films, and agreat deal of research has also been conducted on a process known assilylation. This process involves the vapor deposition of a thin film ofa silicon-containing species on top of a previously deposited organiclayer. This thin film of the silicon species can then be imaged to forma thin film of silicon oxide, which acts as the TSI layer duringoxygen-plasma patterning of the organic layer beneath. The acceptance ofsilylation processes by the semiconductor and packaging industries hasbeen insignificant as a result of a number of process and costlimitations.

[0012] Another use of thin films in semiconductor processing is for theformation of hard masks, e.g., for use in ion implantation processing.Ion implantation is a well known technique used, for example, in formingdoped regions in a substrate during semiconductor fabrication. Ionimplantation frequently requires a patterned blocking layer, also knownas a hard mask, which directs the ions to be implanted only intopredetermined regions. For example, U.S. Pat. No. 5,436,176 to Shimizuet al. discloses, in “Embodiment 1”, maskless implantation of a siliconsubstrate covered by a silicon oxide film, which is disclosed to bethrice-implanted with boron atoms. Alternatively, the same patentdiscloses, in “Embodiment 3”, implantation using multiple hard masks ina thrice-repeated method comprising the following sequence of steps:forming a mask on a silicon substrate covered by a silicon oxide film,implantation with phosphorus, forming a second mask, implantation withboron, and, finally, annealing.

[0013] As previously discussed, formation of a hard mask by any of theseprocesses requires a relatively large number of process steps.Eliminating some of these steps before etching or ion implantation wouldbe beneficial because, for example, it could simplify the process used,increase its efficiency, and/or reduce its cost.

[0014] One approach to solve the problem involves the use of aphotoresist as a mask. However, it is well known that photoresists havelow etch resistance to certain plasma etching chemistries, particularlyfor the patterning of organic layers which may be employed asintermediate protecting layers or which are finding increasing use aslow-dielectric constant (low-k) dielectrics, and low stopping power forions. Therefore, undesirably thick photoresist films are required topermit complete etching of the layer to be patterned prior to completeerosion of the masking layer or to prevent implantation of the areas ofthe substrate onto which they are applied. Another disadvantage is thation implants and photoresists can be exceedingly difficult to removefrom wafers. Other solutions to the problem have been attempted, forexample, by first applying a hard mask, then applying a photoresistlayer atop the hard mask followed by patterning before etching or ionimplantation take place. Combining some of the many steps disclosed inthe prior art methods before plasma etching or ion implantation, or eveneliminating one or more of them, would help simplify these processes.Thus, a method to eliminate steps in a plasma patterning or an ionimplantation process would be highly desirable.

[0015] The photochemical processes for metal complex precursordeposition have been developed as less expensive methods of formingamorphous metal and metal oxide patterns. A precursor is at leastpartially converted to an amorphous metal or metal oxide layer by apartial converting means, e.g., light. As such, the present processesand, specifically, the photochemical metal organic deposition process,has utility in, e.g., the semiconductor and packaging industries.

[0016] The processes of the present invention can provide a patternedhard mask, thus replacing both the oxide and photoresist layers used inconventional TSI and ion implantation methods and, for example,simplifying those methods by reducing the number of processing stepswhich must be performed. Another advantage of this invention is that thematerial which is produced may have better etch resistance to plasmaetching chemistries. This confers still another advantage to the presentprocess that allows for the use of extremely thin films as the hardmask, increasing the ultimate resolution of the lithographic process andallowing the formation of smaller and finer features. A furtheradvantage of this invention is that the material which is produced mayhave better ion implant blocking and stopping power. Additionally, theprocess of the present invention is advantageous in that it facilitatesthe use of new materials for patterned layers, such as platinum,iridium, iridium oxide, ruthenium, ruthenium oxide, and others that areknown in the art to be difficult or impossible to etch by conventionalprocesses.

[0017] At the current state of photochemical metal organic depositiontechnology, processing time is an issue. Exposure times are long andbecome longer as the thickness of the final film of converted precursorincreases. Exposure times may reach one hour or more. In order to ensurewidespread acceptance of the photochemical metal organic depositiontechnology, ways of reducing the processing time must be found,developed, and presented to the customers as part of a complete package.

[0018] The time required to process a layer of precursor is a barrier tohigh production efficiency in the photochemical metal organic depositionprocess. The patterning step in particular is a relatively slow step.What is needed is a way to reduce time required for patterning in thephotochemical metal organic deposition process.

[0019] The following patents address conventional apparati for, andmethods of, transferring wafers, pattern forming, and exposuretechniques.

[0020] U.S. Pat. No. 5,140,366 describes an exposure apparatus forprinting a pattern of a reticle on different shot areas of the wafer ina step-and-repeat manner. In the disclosed apparatus, an image of analignment mark of the reticle is printed, by use of a projection lenssystem, on each of some shot areas of the wafer which are selected asthe subject of detection. By this, a latent image of the reticle mark isformed on each of the selected shot areas. The latent image of thereticle mark is detected by a microscope which may be a phase contrastmicroscope and, from the results of detection concerning all the latentimages of the reticle mark, a reference (correction) grid representingthe coordinate positions of all the shot areas of the wafer is preparedand stored. In accordance with the stored reference grid, the stepwisemovement of the wafer is controlled at the time of the step-and-repeatexposures of the wafer. This allegedly improves throughput of theapparatus. Further, use of the phase contrast microscope for thedetection of the latent image of the reticle mark ensures furtherimprovement in the alignment accuracy.

[0021] U.S. Pat. No. 4,770,590 describes a wafer transfer mechanism usedfor transferring wafers between cassettes and a boat that uses sensorsto detect and to measure any offset of the actual center of each waferbeing transferred with respect to the expected or precalibrated centerof that wafer. An appropriate adjustment is made to effectivelyeliminate such offset so that each wafer can be transferred throughoutthe system without any edge contact between a wafer and the boat or thecassette. The system also includes a boat exchange unit having arotatable turntable which is used in association with two boats. Theboat exchange unit permits a continuous mode operation in which one boatcan be undergoing a loading or unloading of wafers at one station on theturntable while another boat is at or is moving to or from a heatingchamber loading or unloading station on the turntable.

[0022] U.S. Pat. No. 5,534,312 discloses a photoresist-free method formaking a patterned, metal-containing material on a substrate whichincludes the steps of depositing an amorphous film of a metal complex ona surface of a substrate, placing the film in a selected atmosphere, andexposing selected areas of the film to electromagnetic radiation,preferably ultraviolet light and optionally through a mask, to cause themetal complex in the selected areas to undergo a photochemical reaction.However, this reference does not envision use of patterned,metal-containing material as a hard mask to protect underlying layersfrom a plasma etching environment.

[0023] U.S. Pat. No. 5,716,758 describes processes for forming finepatterns on a semiconductor substrate to a lesser degree than theresolving power of a step and repeat, thereby improving the degree ofintegration of the semiconductor device. The process comprises the stepsof: forming a first light-exposure mask and a second light-exposure maskwith interlaced patterns selected from a plurality of fine patterns tobe formed on a semiconductor substrate; coating an organic materiallayer on the semiconductor substrate; patterning the organic materiallayer by use of the first light-exposure mask, to form organic materiallayer patterns; forming a photosensitive film over the organic materiallayer patterns; and patterning the photosensitive film by use of thesecond light-exposure mask to form photosensitive film patterns, in sucha way that each of photosensitive film patterns is interposed betweentwo adjacent organic material layer patterns.

[0024] U.S. Pat. No. 5,935,762 describes a new method for forming dualdamascene patterns using a silylation process. A substrate is providedwith a tri-layer of insulation formed thereon. A first layer ofsilylation photoresist is formed on the substrate and is imaged with ahole pattern by exposure through a mask. Using a silylation process,which greatly improves the depth of focus by reducing reflections fromthe underlying substrate, the regions in the first photoresist adjacentto the hole pattern are affixed to form top surface imaging mask. Thehole pattern is then etched in the first photoresist. A second layer ofphotoresist is formed, and is imaged with a line pattern aligned withthe previous hole pattern by exposure through a mask. The line patternin the second photoresist is etched. The hole pattern in the firstphotoresist is transferred into the top layer of composite insulationfirst and then into the middle etch-stop layer by successive etching.The line pattern in the second photoresist layer is transferred into thefirst photoresist layer through a subsequent resist dry etching process.Finally, the line pattern and the hole pattern are transferredsimultaneously into the top and lower layers of the composite insulationlayer, respectively, through a final dry oxide etching. Having thusformed the integral hole and line patterns into the insulation layer,metal is deposited into the dual damascene pattern. Any excess metal onthe surface of the insulating layer is then removed by any number ofways including chemical-mechanical polishing, thereby planarizing thesurface and readying it for the next semiconductor process.

[0025] U.S. Pat. No. 5,989,759 describes a method where in the case offorming a fine pattern by exposure after exposure of a rough pattern,the exposure position of the rough pattern is adjusted, based on alatent image of the rough pattern, which has been subjected to exposure.As a result, a positional displacement between rough and fine patternsis reduced so that a desired pattern can be formed with high accuracy.To achieve down-sizing and improvements of throughputs, light exposureand charge beam exposure are sometimes used together. In case ofperforming exposure of a desired pattern in a plurality of stages, apositional displacement of each of exposure patterns in the stages leadsto a decrease in exposure accuracy.

SUMMARY OF THE INVENTION

[0026] The present invention relates to a method of converting anorganometallic precursor material to a metal-containing pattern adherentto a substrate, comprising: applying the organometallic precursormaterial in an amount sufficient to coat at least a portion of thesubstrate, wherein said organometallic precursor material is adapted tobe converted to form a metal or metal oxide; pre-converting theorganometallic precursor material by exposing the organometallicprecursor material to a pre-conversion energy exposure dose such thatthe pre-converted precursor material is not converted to a degreesufficient to impair pattern resolution; pattern converting a portion ofthe pre-converted precursor material to convert this portion to apattern-converted material to an extent sufficient to thereby form apattern on the substrate; and either:

[0027] 1) developing the portion of the pre-converted precursor materialthat was not pattern-converted such that the pattern remains on thesubstrate after developing; or alternately,

[0028] 2) pattern converting a second portion of the pre-convertedprecursor material to convert this portion to a pattern-convertedmaterial an extent sufficient to thereby form a second pattern on thesubstrate; and developing the second portion of the pre-convertedprecursor material that was pattern-converted such that the secondpattern remains on the substrate after developing.

[0029] In one embodiment, the pattern conversion comprises exposing thepre-converted precursor material to a patterning energy exposure dose,which converts the pre-converted precursor material to metal or metaloxide that adheres to the substrate to an extent sufficient to therebyform a deposited pattern thereon.

[0030] In another embodiment, the pre-conversion energy exposure dose isselected to be about 20% or less of, alternately from about 20% to about50% of, the combination of the pre-conversion energy exposure dose andthe patterning energy exposure dose, such that the pre-convertedprecursor material is substantially developable.

[0031] In yet another embodiment, the pre-conversion, thepattern-conversion, or both, comprises photochemical metal organicdeposition. In still another embodiment, the pre-conversion comprisesforming a metal or metal oxide within the organometallic precursormaterial.

[0032] In yet another embodiment, the pre-conversion energy exposuredose is selected to be from about 30% to about 80%, alternately fromabout 60% to about 99%, alternately about 50% or more, of a maximumpre-conversion energy exposure dose, wherein the maximum pre-conversionenergy exposure dose is that energy dose above which the organometallicprecursor material exposed to the pre-conversion energy exposure dose isno longer substantially developable or above which the organometallicprecursor material exposed to the pre-conversion energy exposure doseadheres to the substrate to a degree sufficient to impair patternresolution, wherein the organometallic precursor material exposed to thepre-conversion energy exposure dose is substantially developable.

[0033] The invention also relates to a substrate containing a patternedmetal or metal oxide layer formed according to the invention.

[0034] In another embodiment, the pre-conversion comprises exposing theprecursor material to a heat source, and wherein the pattern-conversioncomprises exposing the pre-converted precursor material to a lightsource. In yet another embodiment, the pre-conversion comprises exposingthe precursor material to a heat source, and wherein thepattern-conversion comprises exposing the pre-converted precursormaterial to an electron-beam source. In still another embodiment, thepre-conversion comprises exposing the precursor material to anelectron-beam source, and wherein the pattern-conversion comprisesexposing the pre-converted precursor material to a light source. In yetanother embodiment, the pre-conversion comprises exposing the precursormaterial to a light source, and wherein the pattern-conversion comprisesexposing the pre-converted precursor material to a light source.

[0035] The invention also relates to an apparatus for converting anorganometallic precursor material to a metal-containing film adherent toa substrate formed by a method according to the above-described methods,comprising: a load station to store the substrate before processing; ameans of delivering the substrate between processing steps; apre-convert section, wherein the substrate is coated, if previouslyuncoated, with a sufficient amount of the organometallic precursormaterial and is subjected to a first converting means in either a seriesor parallel arrangement; a pattern convert section, wherein theorganometallic precursor material coated on the substrate, subjected toa first converting means, and not covered by a mask is substantiallyconverted, using a second converting means, to form a metal-containingpattern adherent to the substrate; and an unload station where thepattern-coated substrate is stored after processing. Advantageously, thefirst and second converting means are the same or different, and whereineach comprises a heat source, a light source, a coherent light source, abroadband light source, an electron beam source, or an ion beam source.

[0036] The invention also relates to a method of selecting apre-conversion energy exposure dose and a patterning energy exposuredose to be used in converting an organometallic precursor material to ametal-containing patterned layer comprising at least two patternelements that are adherent to a substrate, which method comprises:determining a relationship between the pre-conversion energy exposuredose in the conversion and the amount of pre-converted precursormaterial that adheres to the substrate; and selecting a pre-conversionenergy exposure dose that is less than a maximum pre-conversion energyexposure dose, wherein the maximum pre-conversion energy exposure doseis that energy dose above which the organometallic precursor materialexposed to the pre-conversion energy exposure dose is no longersubstantially developable or above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose adheres tothe substrate to a degree sufficient to impair pattern resolution, suchthat the patterning energy exposure dose yields an acceptable patternresolution on the substrate, wherein the acceptable pattern resolutionis such that the at least two elements of the metal-containing patternedlayer are discrete and not connected by like material.

[0037] Advantageously, the method can further comprise identifying amaximum pre-conversion energy exposure dose based on the dose-conversionrelationship, such that the organometallic precursor material exposed tothe pre-conversion energy exposure dose, but not to the patterningenergy exposure dose is substantially removable during developing. Inone embodiment, the pre-conversion energy exposure dose is selected tobe about 20% or less, or alternately from about 20% to about 50%, of thecombination of the pre-conversion energy exposure dose and thepatterning energy exposure dose, such that the pre-converted precursormaterial is substantially developable.

[0038] In another embodiment, the pre-conversion energy exposure dose isselected to be from about 30% to about 80%, alternately from about 60%to about 99%, alternately about 50% or more, of a maximum pre-conversionenergy exposure dose, wherein the maximum pre-conversion energy exposuredose is that energy dose above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose is no longersubstantially developable or above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose adheres tothe substrate to a degree sufficient to impair pattern resolution,wherein the organometallic precursor material exposed to thepre-conversion energy exposure dose is substantially developable.

BRIEF DESCRIPTION OF THE DRAWINGS

[0039]FIG. 1 illustrates a basic sequence of a photochemical metalorganic deposition process.

[0040]FIGS. 2 and 3 show two different varieties of a two-stepconversion tool for conversion of precursor on a substrate.

[0041]FIG. 4 illustrates the method steps of a two-step conversion ofprecursor.

[0042]FIG. 5 illustrates the relationship between the pre-conversionexposure dose and the subsequent solubility of the pre-exposed filmafter development.

[0043]FIGS. 6a and 6 b illustrate the relationship betweenpre-conversion exposure dose and pattern conversion exposure dose.

[0044]FIG. 7 illustrates the method steps of selecting pre-conversionexposure dose and pattern exposure dose to be used in the pre-convertsection and the pattern convert section of the dual conversion tool.

[0045]FIG. 8 illustrates the refractive indices of various ZrO₂ filmsformed by thermal and photochemical conversion.

[0046]FIG. 9 shows a thermal contrast curve for a barium strontiumtitanate-forming precursor.

[0047]FIG. 10 shows a photochemical contrast curve for a bariumstrontium titanate-forming precursor.

[0048]FIG. 11 shows a combined thermal/photochemical contrast curve fora barium strontium titanate-forming precursor.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] The invention utilizes a pre-conversion step, which serves topre-convert at least a portion of a precursor material by theapplication of a pre-conversion energy exposure dose. Thispre-conversion energy exposure dose is less than the total exposureenergy dose to which the precursor material is exposed. Thepre-conversion energy exposure dose is beneficially an amount such thatsubstantially no precursor that is not subjected to a subsequentconversion step adheres to the substrate during or after a subsequentdeveloping step.

[0050] Current precursors require a significant amount of exposureenergy, and therefore longer exposure time compared to photoresists. Theinvention relates to a photochemical metal organic deposition patterningprocess that is facilitated by a pre-conversion step. What is needed isa way to increase the throughput of the photochemical metal organicdeposition patterning process by using a pre-conversion step.

[0051] The invention relates to a pre-conversion methodology andcorresponding tool needs to be developed for pre-converting theprecursor without requiring additional capital cost or slowing theproduction process. The invention also relates to an efficientpre-conversion methodology.

[0052] Total exposure energy dose must be distributed betweenpre-conversion dose and final conversion dose. A relationship betweeneach portion of the total exposure dose and desired productcharacteristics is determined to optimize the time saving and achievegood pattern resolution. The invention relates to a method ofdetermining the optimal division between time spent in pre-conversionand patterning (total conversion).

[0053] The present process allows for advantages unavailable with otherfilm deposition and formation methods. As a result, it presents the userwith a greater ability to control and manipulate the characteristics ofthe resulting film to suit the desired application. Therefore, thepresent process is useful in a broad spectrum of applications.

[0054] This invention provides a process for making patterned films ofdesired materials. It is important to recognize that amorphous films aredistinct from polycrystalline and crystalline films; further, whileamorphous films are distinct from more ordered films, in addition,different amorphous films formed by different film-forming methods aredifferent from one another. Further still, the different properties ofdifferent amorphous films formed by different methods can be controlledand engender specific chemical, physical and mechanical properties thatare useful in particular applications.

[0055] Photochemical metal organic deposition is a process thatfacilitates the formation of one or more metal-containing layers thatare adherent to a substrate, generally beginning with an organometallicprecursor material. However, any suitable method for converting anorganometallic precursor material ultimately into a metal-containinglayer that is sufficiently adherent to a substrate and/or that issubstantially not developable may be used. Organometallic precursormaterials, which are defined herein to contain organometallic-ligandmoieties or coordination complexes of ligands with one or more metals,can be synthesized by any known means and may also include a solvent orsolvent mixture to facilitate delivery to the substrate. Subsequentsteps may be undertaken to form a metal-containing film that is adherentto the substrate. These subsequent steps may include some or all of thefollowing: spin or spray application to the substrate, pre-conversiontreatment, conversion, post-conversion treatment, developing, andpost-development treatment. Specific steps chosen can depend upon theultimate end-use of the product. A method of using photochemical metalorganic deposition is given, e.g., in U.S. Pat. No. 5,534,312, whichdescribes a method for directly depositing metal containing patternedfilms, and the entire disclosure of which is hereby incorporated byexpress reference hereto.

[0056] Where a patterned film is desired, the process described here mayproceed photochemically, without the use of an intermediate patterningmaterial, e.g., a photoresist, and may be undertaken under ambientconditions, or may be undertaken under other conditions such as eitheran air or other composition atmosphere and/or under a variety ofpressures, e.g., ambient, higher or lower than ambient, and may be usedin conjunction with a variety of other processing steps to yield uniquematerials.

[0057] Where the process is performed photolytically, the processproceeds at substantially ambient temperatures while other prior artmethods require the use of elevated temperatures to effect patterntransfer, often greater than about 100° C. This limitation conferssevere processing constraints from a manufacturing standpoint and limitsthe choice of materials used in the assembly of devices associated withthe applications of the method.

[0058] The process of the present invention usually proceedssatisfactorily under substantially ambient pressure. In contrast, manyof the prior art deposition methods, in addition to having theaforementioned limitations, must be undertaken under conditions of highvacuum, invoking the necessity for expensive and complicated equipmentthat is difficult to run and maintain.

[0059] The processes of the present invention facilitate the formationof a thin layer on a substrate from a precursor material, preferably anorganometallic precursor material. The precursor material comprisesmolecules specifically designed for their ability to coat the substratein a uniform manner, resulting in films of high optical quality, and, inthe case of the present process, for photosensitivity. The identity ofthe precursor molecule is a significant variable—a wide variety of metalcomplexes of the formula M_(a)L_(b) comprising at least one metal (“M”),i.e., a is an integer which is at least 1, and at least one suitableligand (“L”) or ligands, i.e., b is an integer which is at least 1, areenvisioned by this invention.

[0060] If a plurality of metals are used, all of the metal atoms may beidentical, all may be different atoms and/or have different valences,e.g., Ba Na or Fe(II) Fe(III), or some may be identical while others maybe different atoms and/or have different valences, e.g., Ba₂ Fe(II)Fe(III). In any case, metal M may be an alkali or alkaline earth, forexample Ba or Li, a transition metal, for example Cr or Ni, a main groupmetal, for example Al or Sn, or an actinide, for example U or Th.Preferably, each metal is independently selected from Li, Al, Si, S(when it has a +6 oxidation state), Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn,Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf, Ta,W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, and Mg.

[0061] If a plurality of ligands are used, all of the ligands may beidentical, all may be different, or some may be identical while othersmay be different. In any case, ligand L is chosen so that asubstantially unconverted precursor complex can be formed and has theproperties that:

[0062] 1) it can be converted into a form such that an adherent layer isdeposited on a substrate,

[0063] 2) the complex is stable or, at least, metastable,

[0064] 3) upon absorbing energy, e.g., one or more photons of therequired energy, the complex can be transformed into a differentmetal-containing moiety through a chemical reaction, and

[0065] 4) any byproducts of the energy-induced chemical reaction shouldbe removable, i.e., should be sufficiently chemically volatile ormechanically labile so as to be removable.

[0066] To achieve the first two of these results, the complex shouldgenerally have a low polarity and low intermolecular forces. As organicgroups usually have low intermolecular forces, ligands having organicgroups at their outer peripheries tend to be satisfactory with respectto the first two requirements. If the energy absorbed is light, thechemical reaction of step (3) is known as a photo-induced reaction.

[0067] The deposited film of substantially unconverted precursor isamorphous or at least substantially amorphous. Therefore, to make themetal complex resistant to crystallization, ligand(s) L preferably aresuch that the complex is asymmetric. The complex may be made asymmetricby using a ligand which itself has two or more stereoisomeric forms. Forexample, if L is racemic 2-ethylhexanoate, the resulting metal complexis asymmetric because the complex has several different stereoisomericforms. The size and shapes of organic portions of the ligands may beselected to optimize film stability and to adjust the thickness of filmthat will be deposited by the selected film deposition process.

[0068] The stability of an amorphous film with respect tocrystallization may also be enhanced by making the film of a complexwhich has several different ligands attached to each metal atom. Suchmetal complexes have several isomeric forms. For example, the reactionof CH₃HNCH₂CH₂NHCH₃ with a mixture of a nickel(II) salt and KNCS leadsto the production of a mixture of isomers. The chemical properties ofthe different isomers are known not to differ significantly, however,the presence of several isomers in the film impairs crystallization ofthe complex in the film.

[0069] The complex must also be stable, or at least metastable, in thesense that it will not rapidly and spontaneously decompose under processconditions. The stability of complexes of a given metal may depend, forexample, upon the oxidation state of the metal in the complex. Forinstance, Ni(0) complexes are known to be unstable in air while Ni(II)complexes are air-stable. Consequently, a process for depositing Nibased films which includes processing steps in an air atmosphere shouldinclude a Ni(II) complex in preference to a Ni(0) complex.

[0070] Partial conversion and conversion result from a chemical reactionwithin the film which changes the partially converted or convertedregions into a desired converted material. Ideally, at least one ligandshould be reactive and be attached to the complex by a bond which iscleaved when the complex is raised to an excited state by the influenceof the partial converting means and/or the converting means. Preferablythe reactive group is severed from the complex in a photochemicalreaction initiated by light, more preferably, by ultraviolet light, asthe partial converting means and/or the converting means. To make suchphotochemical step(s) in the process efficient, it is highly preferablethat the intermediate product produced when the reactive group issevered be unstable and spontaneously convert to the desired newmaterial and volatile byproduct(s).

[0071] There are several mechanisms by which a suitable photochemicalreaction may occur. Some examples of suitable reaction mechanisms whichmay be operable, individually or in combination, according to theinvention are as follows: (a) absorption of a photon may place thecomplex in a ligand to metal charge transfer excited state in which ametal-to-ligand bond in the metal complex is unstable, the bond breaksand the remaining parts of the complex spontaneously decompose, (b)absorption of a photon may place the complex in a metal-to-ligand chargetransfer excited state in which a metal-to-ligand bond in the complex isunstable, the bond breaks and the remaining parts of the complexspontaneously decompose, (c) absorption of a photon may place thecomplex in a d-d excited state in which a metal-to-ligand bond in thecomplex is unstable, the bond breaks and the remaining parts of thecomplex spontaneously decompose, (d) absorption of a photon may placethe complex in an intramolecular charge transfer excited state in whicha metal-to-ligand bond in the complex is unstable, the bond breaks andthe remaining parts of the complex spontaneously decompose, (e)absorption of a photon may place at least one ligand of the complex in alocalized ligand excited state, a bond between the excited ligand andthe complex is unstable, the bond breaks and the remaining parts of thecomplex spontaneously decompose, (f) absorption of a photon may placethe complex in an intramolecular charge transfer excited state such thatat least one ligand of the complex is unstable and decomposes, then theremaining parts of the complex are unstable and spontaneously decompose,(g) absorption of a photon may place at least one ligand of the complexin a localized ligand excited state wherein the excited ligand isunstable and decomposes, then the remaining parts of the complex areunstable and spontaneously decompose, and (h) absorption of a photon mayplace the complex in a metal-to-ligand charge transfer excited state inwhich at least one ligand of the complex is unstable and decomposes,then the remaining parts of the complex are unstable and spontaneouslydecompose. In its broad aspects, however, this invention is not to beconstrued to be limited to these reaction mechanisms.

[0072] More preferably, the ligands are selected from the groupconsisting of acetylacetonate (also known as “acac” or 2,4-pentanedione)and its anions, substituted acetylacetonate, i.e.,

[0073] and their anions, acetonylacetone (also known as 2,5-hexanedione)and its anions, substituted acetonylacetone, i.e.,

[0074] and its anions, dialkyldithiocarbamates, i.e.,

[0075] and its anions, carboxylic acids, i.e.,

[0076] such as hexanoic acid where R=CH₃(CH₂)₄, carboxylates, i.e.,

[0077] such as hexanoate where R=CH₃(CH₂)₄, pyridine and/or substitutedpyridines, i.e.,

[0078] azide, i.e., N₃ ⁻, amines, e.g., RNH₂, diamines, e.g., H₂NRNH₂,arsines, i.e.,

[0079] diarsines, i.e.,

[0080] phosphines, i.e.,

[0081] diphosphines, i.e.,

[0082] arenes, i.e.,

[0083] hydroxy, i.e., OH⁻, alkoxy ligands, e.g., RO⁻, ligands such as(C₂H₅)₂NCH₂CH₂O—, alkyl ligands, e.g., R⁻, aryl ligands, and mixturesthereof, where each R, R′, R″, R′″, and R″″ is independently selectedfrom organic groups and, preferably, is independently selected fromalkyl, alkenyl, aralkyl and aralkenyl groups.

[0084] As used herein, the term “alkyl” refers to a straight or branchedhydrocarbon chain. As used herein, the phrase straight chain or branchedchain hydrocarbon chain means any substituted or unsubstituted acycliccarbon-containing compounds, including alkanes, alkenes and alkynes.Examples of alkyl groups include lower alkyl, for example, methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl oriso-hexyl; upper alkyl, for example, n-heptyl, -octyl, iso-octyl, nonyl,decyl, and the like; lower alkylene, for example, ethylene, propylene,propylyne, butylene, butadiene, pentene, n-hexene or iso-hexene; andupper alkylene, for example, n-heptene, n-octene, iso-octene, nonene,decene and the like. The ordinary skilled artisan is familiar withnumerous straight, i.e., linear, and branched alkyl groups, which arewithin the scope of the present invention. In addition, such alkylgroups may also contain various substituents in which one or morehydrogen atoms is replaced by a functional group or an in-chainfunctional group.

[0085] As used herein, the term “alkenyl” refers to a straight orbranched hydrocarbon chain where at least one of the carbon-carbonlinkages is a carbon-carbon double bond. As used herein, the term“aralkyl” refers to an alkyl group which is terminally substituted withat least one aryl group, e.g., benzyl. As used herein, the term“aralkenyl” refers to an alkenyl group which is terminally substitutedwith at least one aryl group. As used herein, the term “aryl” refers toa hydrocarbon ring bearing a system of conjugated double bonds, oftencomprising at least six π (pi) electrons. Examples of aryl groupsinclude, but are not limited to, phenyl, naphthyl, anisyl, toluyl,xylenyl and the like.

[0086] The term “functional group” in the context of the presentinvention broadly refers to a moiety possessing in-chain, pendant and/orterminal functionality, as understood by those persons of ordinary skillin the relevant art. As examples of in-chain functional groups may bementioned ethers, esters, amides, urethanes and their thio-derivatives,i.e., where at least one oxygen atom is replaced by a sulfur atom. Asexamples of pendant and/or terminal functional groups may be mentionedhydrogen-containing groups such as hydroxyl, amino, carboxyl, thio andamido, isocyanato, cyano, epoxy, and ethylenically unsaturated groupssuch as allyl, acryloyl and methacryloyl, and maleate and maleimido.

[0087] To enhance the desired photochemical characteristics, includingthe tendency of the products of the photochemical reaction tospontaneously thermally decompose, ligands comprising and/or selectedfrom one or more of the following groups may be used alone or incombination with the above-listed ligands: oxo, i.e.,

O₂ ⁻

[0088] oxalato, i.e.,

[0089] halide, hydrogen, hydride, i.e., H⁻, dihydride, i.e., H₂,hydroxy, cyano, i.e., CN⁻, carbonyl, nitro, i.e., NO₂, nitrito, i.e.,NO₂ ⁻, nitrate, i.e, NO₃, nitrato, i.e., NO₃ ⁻, nitrosyl, i.e., NO,ethylene, acetylenes, i.e.,

R≡R′

[0090] thiocyanato, i.e., SCN⁻, isothiocyanato, i.e., NCS⁻, aquo, i.e.,H₂O, azides, carbonate, i.e., CO₃ ⁻², amine, and thiocarbonyl, whereeach R and R′ is independently selected from organic groups and,preferably, is independently selected from alkyl, alkenyl, aralkyl andaralkenyl groups. Even more preferably, each ligand is independentlyselected from acac, carboxylates, alkoxy, oxalato, azide, carbonyl,nitro, nitrato, amine, halogen and their anions.

[0091] Preferably, the metal complex precursor is selected from thosecomprising acac, carboxylato, alkoxy, azide, carbonyl, nitrato, amine,halide and nitro complexes of Li, Al, Si, Ti, V, Cr, Mn, Fe, Ni, Co, Cu,Zn, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, In, Sn, Ba, La, Pr, Sm, Eu, Hf,Ta, W, Re, Os, Ir, Pt, Au, Pb, Th, U, Sb, As, Ce, Mg, and mixturesthereof

[0092] The precursor may be applied to the substrate directly.Alternatively and preferably, the precursor is dissolved in a solvent orsolvents to form a precursor solution. This facilitates its applicationto the substrate by a variety of means well known to those of ordinaryskill in the art, such as by spin or spray application of the solutionto the substrate. The solvent may be chosen based on several criteria,individually or in combination, including the ability of the solvent todissolve the precursor, the inertness of the solvent relative to theprecursor, the viscosity of the solvent, the solubility of oxygen orother ambient or other gases in the solvent, the UV, visible, and/orinfrared absorption spectra of the solvent, the absorption cross-sectionof the solvent with respect to electron and/or ion beams, the volatilityof the solvent, the ability of the solvent to diffuse through asubsequently formed film, the purity of the solvent with respect to thepresence of different solvent isomers, the purity of the solvent withrespect to the presence of metal ions, the thermal stability of thesolvent, the ability of the solvent to influence defect or nucleationsites in a subsequently formed film, and environmental considerationsconcerning the solvent. Exemplary solvents include the alkanes, such ashexanes, the ketones, such as methyl isobutyl ketone (“MIBK”) and methylethyl ketone (“MEK”), and propylene glycol monomethyl ether acetate(“PGMEA”).

[0093] The concentration of the precursor in the solution may be variedover a wide range and may be chosen by one of ordinary skill in the artwith, at most, minimal routine experimentation, such that the propertiesof the precursor film, including its thickness and/or sensitivity toirradiation by light or particle beams, are appropriate for the desiredapplication.

[0094] To the extent that metal atoms in the patterned layer or filmformed by a method according to the invention might be “bumped” into theunderlying substrate during a subsequent step, this can be overcome bycareful selection of precursor formulation conditions and/or thickness.Alternatively, an optional protective layer can be used between thesubstrate and the precursor layer which remains to protect the substrateafter the patterned layer forming process is completed. Optionally, thesubstrate may be coated with at least one protective layer before theprecursor or precursor solution is applied. The protective layer may beapplied to the substrate by a variety of means well known to those ofordinary skill in the art. Protective layers are particularly desirablewhen the process includes an ion implantation step.

[0095] The preparation of the substrate prior to deposition of theprecursor film can have a significant impact on the ultimate nature ofthe desired patterned layer. Thus, certain surface preparations may bedesirable or, conversely, may need to be avoided depending upon theparticular patterned layer used. Substrate preparations may include asimple cleaning process to remove unwanted species from the substratesurface, a prior patterning step, the deposition of a barrier material,the deposition of an adhesion promoting material, or the deposition of areactive material designed to induce chemical change in the film ofdeposited material, e.g., a coupling agent.

[0096] The method of application of the precursor or the precursorsolution may be chosen depending on the substrate and the intendedapplication. Some examples of useful coating methods well known to thoseof ordinary skill in the art include spin, spray, dip and rollercoating, stamping, meniscus, and various inking approaches, e.g.,inkjet-type approaches. Variables in the coating process may be chosenin order to control the thickness and uniformity of the deposited film,to minimize edge effects and the formation of voids or pinholes in thefilm, and to ensure that no more than the required volume of precursoror precursor solution is consumed during the coating process. Optimizedapplication of the precursor film may desirably yield very smooth films.

[0097] The deposited film may, optionally, be subjected to a baking orvacuum step where any residual solvent present in the deposited film maybe driven off. If a baking step is employed, it is, of course, importantto keep the temperature of this step below the temperature at which theprecursor molecules decompose thermolytically. The process of theinvention allows for blanket thermal or heat treatment or annealing ofthe precursor cast film so as to convert it thermolytically into ablanket uniform coating of the desired material, or to a film thatrequires a lower partial converting means and/or converting means dosefor patterning than would have been possible without the thermaltreatment. The deposited film may optionally be subjected to othertreatments at this stage of the process, including but not limited toblanket photochemical or electron beam exposure and microwave treatment.

[0098] Typically, baking off solvent does not initiate pre-conversion.It is recognized, however, that a bake step during the process maycontribute to ejecting solvent from the precursor film and also initiatea thermal decomposition process. Both of these mechanisms may aid in theoverall efficiency of the process resulting in, for example, a lowerdose requirement during a subsequent converting step. It is furtherrecognized that during such a bake step, a new pre-converted material,different from either the deposited film or the film of the desiredmaterial, may be formed. The effect of this could alter subsequentproperties of the desired material, including dielectric constant,nucleation, speciation, and crystallization behavior in ways that arenot readily predicted by one skilled in the art. For example, a twocomponent system in which one material is activated in the pre-bake stepwhile the other component(s) is selected to be activated in either aphotochemical or higher energy thermal process step may be preferred incertain applications. This deposition, from a mixture of precursors,would permit the efficient design of a system to take advantage of thedifferent chemical properties of materials formed from the bake andsubsequent partial converting and/or converting step(s).

[0099] The deposited film is subjected to a pre-conversion stepincluding a partial converting means and/or converting means, i.e., asource of energy, such that the precursor is at least partiallyconverted. The entire film, or selected regions of the depositedprecursor film, may be exposed to a source of energy. The energy sourcemay be, e.g., a heat source, a light source of a specific wavelength, acoherent light source of a specific wavelength or wavelengths, abroadband light source, an electron beam (“e-beam”) source, or an ionbeam source, or a combination thereof. Light in the wavelength range offrom about 150 to about 600 nm is suitably used. Preferably, thewavelength of the light is from about 157 to about 436 nm.

[0100] In certain embodiments of the invention, the energy source is alight source directed through an optical mask used to define an image onthe surface. The mask consists of substantially transparent andsubstantially opaque or light absorbing regions. The mask may alsoinclude an optical enhancing feature such as a phase shift technology.The mask typically has opaque regions and transparent regions, relativeto the patterning light, so that only portions of the photosensitivelayer are exposed, from which a pattern is formed. The exposure canchange the solubility and/or composition of the exposed areas of thephotosensitive layer in such a manner that either the exposed orunexposed areas may be selectively removed by use of a developingsolution. The remaining material can consist essentially of: organicmaterial, in a first embodiment; dielectric material, in a secondembodiment; and metal and/or metal oxide, in a third embodiment.However, the energy source need not be directed through a mask. Forexample, if it is not necessary to pattern the material, a flood orblanket energy exposure may be used, such as is provided by thermalenergy or a wide beam of light.

[0101] The atmosphere and pressure, both total and partial, under whichthe deposited film is at least partially converted may be importantprocess variables. Normally, it is convenient and economical for theatmosphere to be air but it may be preferable to change the compositionof the atmosphere present during at least partial conversion. One reasonfor this is to increase the transmission of the exposing light, if shortwavelength light is used, because such light may be attenuated by air.Similarly, electron-beam radiation may be impaired by the presence ofcertain gases. It may also be desirable to change the composition of theatmosphere to alter the composition or properties of the product film.For example, the exposure of a copper complex results in the formationof a copper oxide in air or oxygen atmospheres. By virtually eliminatingoxygen from the atmosphere, a film comprising primarily reduced copperspecies may be formed. For example, a partial conversion or conversionstep is preferably performed in the presence of oxygen if the convertedprecursor is to be a dielectric film or in the presence of a reducinggas, such as hydrogen, if the converted precursor is to be a metallicfilm. Additionally, the amount of water in the film may be changed bychanging the humidity of the atmosphere. By increasing the intensity ofthe light, it is possible to initiate thermal reaction within the filmsto generate product films.

[0102] The use of a partial conversion step, or different partialconversion steps in sequence, also known as “substrate pretreatment,”may be advantageous from a process flow standpoint, for example, inorder to minimize the time during which a precursor atop a substrateneeds to be exposed in an expensive piece of equipment, such as astepper or masked light. Substrate pretreatment is preferred in methodsaccording to the present invention.

[0103] After the precursor has been pre-converted, a portion of theprecursor film is next optionally but typically subjected to aconverting means such that the desired portion(s) of the precursoris(are) substantially converted. The entire film or selected regions ofthe precursor film may be exposed to a source of energy. Preferably, themethods according to the present invention include substantiallyconverting only a portion of the precursor material, generally in theshape of a predetermined pattern, which may be outlined by an externalmask. In this preferred embodiment, the remaining portion of theprecursor material should generally remain partially converted such thatthe pattern resolution is not impaired. Optionally but preferably, theremaining portion of the precursor material should be substantiallydevelopable, while the substantially converted portion of the precursormaterial, referred to herein as the pattern-converted material, shouldbe substantially undevelopable and/or sufficiently adherent to thesubstrate.

[0104] In one embodiment, unconverted and/or partially convertedprecursor is/are removed during development. In another embodiment, thedeveloping material is selected so that unconverted and/or partiallyconverted precursor material is/are not removed during the development,but the pattern-converted precursor material is removed duringdevelopment.

[0105] The converting means can be an energy source that may be the sameas or different from any partial converting means previously employed.For example, the converting means may be a light source of a specificwavelength, a coherent light source of a specific wavelength, abroadband light source, an electron beam source, or an ion beam source.In certain embodiments of the invention, the energy source is a lightsource directed through an optical mask used to define an image on thesurface, as discussed above. However, the energy source need not bedirected through a mask. For example, it may not be necessary to patternthe material during the conversion step, e.g., because the precursor mayalready be patterned, therefore, a flood or blanket exposure may be usedas the converting means. Preferred converting means include light,electron beam, ion beam, and thermal treatment. As discussed above forpartial conversion and as is also applicable here, the atmosphericconditions under which the deposited film is converted, such asatmosphere composition, pressure, both total and partial, and humidity,may be important process variables. During conversion, these variablesmay be the same as or different from their settings used in anypreceding partial conversion step.

[0106] Following substantial conversion of a portion of the precursorinto a patterned layer or film, the precursor film may, optionally, betreated by any of a variety of methods well known to the art prior toremoving at least a portion of the unconverted precursor layer. Thesemethods include but are not limited to annealing treatments, such asthermal, laser or plasma annealing steps, exposure to a specificatmosphere, e.g., oxidizing or reducing, ion implantation, microwavetreatment and electron beam treatment. If the at least partial convertedarea(s) may serve as electroless plating nucleation sites relative tothe unconverted area(s) of the precursor, then an optional plating stepmay be used at this stage.

[0107] Unexposed or insufficiently converted or adherent regions of theprecursor layer, or portions thereof, may then be removed by theapplication of a removing (or developing) means. For example, adeveloping means may comprise a developer composition that may beapplied as a liquid or a solution in a puddle development or immersionwet development process. Alternately, a dry development processanalogous to dry patterning steps conventionally employed by thesemiconductor industry may be employed as a developing means. Preferredremoval means include spray development, puddle development, andimmersion wet development.

[0108] The developer should typically be formulated and/or used underconditions such that a solubility difference exists between exposed andunexposed regions of the film. This solubility difference is used toremove preferentially select regions of the film such that certainchosen regions of the film are substantially removed by the developerwhile regions desired to remain on the substrate are left substantiallyintact. The precursor and developer are selected so that either of thepre-converted or the pattern-converted precursor materials is removedduring development. Considerable experimentation may be required tooptimize the formulation of the developer. For example, in a process inwhich regions that have been exposed to incident energy are desired toremain on the substrate, use of the casting solvent to develop the filmafter exposure to incident radiation is too aggressive. A dilutesolution of the casting solvent in another liquid in which (a) thecasting solvent is miscible, (b) unexposed regions of the film aresparingly (but not necessarily completely) soluble, and (c) exposedregions of the film are substantially insoluble, provides for animproved development process.

[0109] After development, the at least partially converted precursormay, optionally, be treated by any of a variety of methods well known tothe art prior to its being subjected to a converting means. Thesemethods include but are not limited to annealing treatments, such asthermal, laser or plasma annealing. The temperature and time of suchannealing are important variables. The annealing step may also beinfluenced by prior surface treatments, for example, oxygen plasma,laser or a rapid thermal annealing (“RTA”) process. It is possible toselect appropriate conditions such that the annealed at least partiallyconverted precursor retains its amorphous nature while at least one ofits physical or electrical properties is desirably altered.Alternatively, annealing conditions that cause the film to convert toits crystalline state, e.g., a high temperature, may be desirabledepending on the application for which the film is to be used. Forexample, appropriate thermal treatment at this stage may be employed toinduce the formation of highly oriented crystalline films from theamorphous at least partially converted precursor. In this manner, theproperties of the amorphous film may be finely tuned or its physicalproperties may even be varied over a wide range—from the completelyamorphous phase at one extreme to semi-crystalline intermediate phasesto a single oriented crystalline phase at the other extreme.

[0110] After conversion, subsequent optional process steps may includepost-conversion treatment, developing, including but not limited to thenovel development method discussed above, and post-developing treatmentsteps. The specific steps chosen depend upon the ultimate use of theproduct. For example, methods of use are described in U.S. Pat. Nos.5,534,312, 5,821,017 and 6,071,676, each of which is incorporated hereinby reference in its entirety.

[0111] In certain embodiments of the present process, conversion isfollowed by an implantation step, where at least one implanted region isformed in the substrate by using an implantation means on at least aportion of the substrate substantially uncovered by the patterned layer.The use of an ion beam as an implantation means is well known to theart. However, the present process is not limited to the use of ionbeams; any effective method of implantation may be used. Ions suitablefor implantation include but are not limited to arsenic, boron andphosphorous. Ion implantation may be conducted under conditions of highenergy, i.e., greater than about 300 KeV, coupled with low dose, i.e.,less than about 10²⁰ atm/cm², or under conditions of low energy, i.e.,less than about 300 KeV, coupled with high dose, i.e., greater thanabout 10²⁰ atm/cm². Optionally, the patterned layer may be removed afterimplantation. Optionally, the implanted substrate may be furthertreated, such as by annealing, thereby converting implanted substrateregions into doped regions. If both of these optional steps areperformed, the order in which they are performed may be adjusted to suitthe particular application to which the present invention is directed.

[0112] Another aspect of the present invention relates to an apparatusfor two-step conversion of an organometallic precursor material to ametal-containing film adherent to a substrate, containing: a loadstation to store the substrate before processing; a means of deliveringthe substrate between processing steps; a pre-convert section, whereinthe substrate is coated, if previously uncoated, with a sufficientamount of the organometallic precursor material and is subjected to afirst converting means in either a series or parallel arrangement; apattern convert section, wherein the organometallic precursor materialcoated on the substrate, subjected to a first converting means, and notcovered by a mask is substantially converted, using a second convertingmeans, to form a metal-containing pattern adherent to the substrate; andan unload station where the pattern-coated substrate is stored afterprocessing. The first and second converting means may be the same ofdifferent, and each encompasses an energy source, which may includelight, UV, thermal, e-beam, or plasma sources.

[0113] Another aspect of the present invention involves a method ofselecting a pre-conversion exposure dose and a pattern exposure dose tobe used in a two-step conversion of precursor on a substrate via aphotochemical metal organic deposition process, and includes the stepsof: experimentally determining percent material converted vs.pre-conversion exposure dose; selecting a maximum pre-conversionexposure dose; and determining the pattern exposure dose that givesacceptable pattern resolution.

[0114] Although the present invention may require preparatory work toexperimentally develop necessary curves to determine the proper balanceof pre-exposure dose and pattern exposure dose, the benefits realizedafter the initial preparatory work, however, outweigh the cost andinconvenience of developing the curves. In addition, the presentinvention enhances the marketability of current precursor material,without requiring new processing tools. The cost saving achieved byeliminating the process steps not required by the photochemical metalorganic deposition process, therefore, can be maintained.

[0115]FIG. 1 illustrates a basic sequence of Photochemical metal organicdeposition process steps in steps 1A, 1B, 1C, and 1D, conducted on asubstrate 10 (shown in step 1A of FIG. 1 prior to photochemical metalorganic deposition processing). Substrate 10 may be a silicon wafer, ormay be another material such as a printed circuit board or a ceramicsubstrate. In step 1B, a precursor 11 is applied to a substrate 10. Instep 1C, light or heat energy is applied to create a converted precursor12 from a selected portion of precursor 11. In step ID, developer isapplied to remove unconverted precursor 11 and leave the convertedprecursor 12 intact.

[0116] The present invention involves an apparatus for undertaking, andmethod of using, a pre-conversion step in the photochemical metalorganic deposition process. The pre-conversion step (partial conversionprior to patterning) can advantageously be performed to reduce theexposure time required while still achieving an acceptable image patternon the substrate.

[0117]FIG. 2 shows a two-step conversion tool 100 for conversion ofprecursor on a substrate, which includes a load station 105, apre-convert section 110, a pattern convert section 115, and an unloadstation 120. A first substrate carrier 125, located at load station 105,delivers a substrate 130 to an airtrack 135 from a stack of substratesstored in first substrate carrier 125. The airtrack 135 delivers asubstrate 130 to one of three (in this example) identical and parallelsub-sections in pre-convert section 110. Pre-convert section 110includes a first hotplate 140 under a first lamp 142, a second hotplate150 under a second lamp 152 and a third hotplate 160 under a third lamp162. Substrates 130 are exposed to light, heat, or both energy forms atthese locations, and then delivered to pattern convert section 115 viaairtrack 135. The number of pre-convert subsections is chosen to matchthe ratio between pre-conversion exposure and pattern exposure. In thepresent example the pre-conversion exposure takes three times as long asthe pattern expose, so a first substrate from first hotplate 140 wouldbe moved to an alignment stage 165 and backfilled by a substrate 130from first substrate carrier 125. After the first substrate is patternedand moved to second substrate carrier 125, a second substrate 130 ismoved from second hotplate 150 to alignment stage 165 and back-filled byanother substrate 130 from first substrate carrier 125. This movementcontinues until all substrates 130 have been through one sub-section ofpre-convert section 110 and pattern convert section 115. The flow ofsubstrates from the sub-sections of pre-convert section 110 to patternconvert section 115 is continuous. Once substrate 130 arrives at patternconvert section 115, it is positioned on alignment stage 165 andsubjected to energy emanating from high intensity lamp 170. The lightenergy from high intensity lamp 170 is directed through a mask 175 andoptics 180 to strike substrate 130. As a result, substrate 130 ispatterned with the shape of mask 175. Substrate 130 then proceeds viaairtrack 135 to unload station 120, where it is moved into substratecarrier 125 and stored to await further processing.

[0118] In another embodiment, the sub-sections of the pre-convertsection are arranged in series rather than in parallel.

[0119]FIG. 3 shows a two-step conversion tool 200 for conversion ofprecursor on a substrate, which includes a load station 205, apre-convert section 210, a pattern convert section 215, and an unloadstation 220. A first substrate carrier 225, located at load station 205,delivers substrate 130 to an airtrack 230 from a stack of substratesstored in first substrate carrier 225. The airtrack 230 deliverssubstrate 130 to pre-convert section 210, where substrate 130 isdelivered to first hotplate 240 under first lamp 235, then to secondhotplate 250 under second lamp 245, and then to third hotplate 250 underthird lamp 255, where substrate 130 is exposed to light, heat, or bothenergy forms at these locations. Substrate 130 proceeds throughpre-convert section 210 to pattern convert section 215 via airtrack 230in a continuous flow. Once substrate 130 arrives at pattern convertsection 215, it is positioned on alignment stage 265 and subjected toenergy emanating from high intensity lamp 270. The light energy fromhigh intensity lamp 270 is directed through a mask 275 and optics 280 tostrike substrate 130. As a result, substrate 130 is patterned with theshape of mask 275. Substrate 130 then proceeds via airtrack 230 tounload station 220, where it is moved into substrate carrier 225 andstored to await further processing.

[0120]FIG. 4 shows the method steps of a two-step conversion ofprecursor, and includes:

[0121] Step 400: Applying precursor

[0122] In this step, the precursor/solvent mix is applied to thesubstrate, for example, by conventional methods such as spin or spraycoating.

[0123] Step 410: Pre-baking

[0124] Excess solvent and/or other volatile components can be removedfrom the substrate, for example, either via a conventional drying ovenor via evaporation.

[0125] Step 420: Pre-converting (exposing)

[0126] Lamps and/or hot plates (as shown in FIGS. 1 and 2) can supplylight and/or heat energy to partially convert the precursor.

[0127] Step 430: Pattern conversion

[0128] Upon exposure to a high intensity lamp through a mask, as shownin FIGS. 1 and 2, the partially converted portions of the precursor canbe further, preferably completely, converted and patterned, e.g., toamorphous metal or metal oxide. Other potential energy sources include athermal, UV, e-beam, or plasma source, and these sources may be used invaried atmospheres (e.g., a vacuum or an inert atmosphere).

[0129] Step 440: Developing

[0130] The patterned substrates can be developed, e.g, via dipping orspraying with solvent to wash away unconverted precursor material.

[0131] Step 450: Post-processing

[0132] Additional steps may be performed if necessary to complete thepresent fabrication level.

[0133]FIG. 5 illustrates the relationship between the pre-conversionexposure dose and the subsequent solubility of the pre-exposed film (ina suitable developer) after that step. The shaded area representspre-conversion doses that will not cause complete conversion. The dottedline indicates the best pre-conversion exposure dose that can beselected to maximize the dose without causing complete conversion of theprecursor. This dose saves the greatest amount of time in the process.However, the selected pattern dose must also yield a high-resolutionimage. This determination requires additional analysis and is describedbelow.

[0134]FIGS. 6a and 6 b illustrate the relationship betweenpre-conversion exposure dose and pattern conversion exposure dose. Thecurve shown in FIG. 6a is the curve of acceptable pattern resolution.Any point lying above the curve in FIG. 6a represents a process thatwould yield a fully converted film (i.e., material with no solubility ina suitable developer). The pre-conversion exposure dose is selected sothat the sum of the pre-conversion exposure dose and the patternconversion exposure dose (“dose to clear”) should substantially convertthe selected precursor material. FIG. 6b illustrates what some regionsof the curve mean in terms of pattern resolution. At a very lowpre-conversion exposure dose, insufficient pre-conversion occurs.Although acceptable pattern resolution can be achieved at that dose,little time is saved in this region under those circumstances. The zeroslope region in the middle of the curve offers the ideal range ofpre-conversion exposure dose and acceptable pattern resolution becauseit maximizes the pre-conversion exposure dose and minimizes the patternexposure dose. If the pre-conversion exposure dose is too high, theprecursor can be overdeveloped and may not be able to be patterned withan acceptable resolution.

[0135]FIG. 7 illustrates the method steps of selecting pre-conversionexposure dose and pattern exposure dose to be used in the pre-convertsection and the pattern convert section of the dual conversion toolshown in FIGS. 2 and 3 above. The steps include:

[0136] Step 700: Experimentally determining percent material convertedvs. pre-conversion exposure dose

[0137] In this step, a specific precursor material is used to determinethe percent precursor material converted for varying pre-conversionexposure doses. The experimental results are used to create a graphsimilar to the one shown in FIG. 5 above.

[0138] Step 710: Selecting maximum pre-conversion exposure dose

[0139] Using the graph developed in Step 700 above, a pre-conversionexposure dose is selected to maximize the dose but not exceed the dosewhere bulk conversion of the precursor material occurs.

[0140] Step 730: Determining Pattern exposure dose that gives acceptablepattern resolution

[0141] A new set of curves is developed to indicate the relationshipbetween pre-conversion exposure dose and pattern conversion exposuredose, as shown in FIGS. 6a and 6 b. Using a specific precursor and aspecific pre-conversion exposure dose, a series of substrates withapplied precursor are converted and developed at varying patternexposure doses and the resultant pattern resolution is measured. Thepoint at which good resolution first occurs is the pattern conversionexposure dose to be shown on the curve (called the “curve of acceptablepattern resolution” in FIGS. 6a and 6 b). The experiment is repeatedusing varying pre-conversion exposure doses until the curve is complete.

[0142] Using the curve, an appropriate pattern exposure dose isdetermined based on the chosen pre-conversion exposure dose. A patternexposure dose and a pre-conversion exposure dose that corresponds to apoint on the curve should yield a good quality image with adequateresolution.

[0143] As used herein, depositing of metal or metal oxide on a substratemeans that a layer of metal or metal oxide is formed and is sufficientlyadherent to the substrate.

[0144] It is understood, of course, that by “substantially developable”is meant that the extent to which the material is developable issufficient to result in a pattern after development which meets allmandated specifications for which the pattern is to be employed. Thesespecifications may include, but are not limited to, dimensionalspecifications (thickness, spatial resolution, surface roughness,sidewall profile and roughness, and others), and materialsspecifications (physical, optical, electrical, magnetic and otherproperties).

[0145] Also, as used herein, the terms “patterning conversion” and“patterning energy exposure dose” refer to using a converting meansaccording to the invention such that the material to be patterned isexposed to a dose of energy sufficient to convert about 80%, preferablyabout 95%, more preferably about 99%, of the precursor material to metalor metal oxide. Energy above or beyond that sufficient to convert about80%, preferably about 95%, more preferably about 99%, of the precursormaterial to metal or metal oxide is generally not considered part ofpattern conversion. When more than one pattern conversion is undertaken,the pattern conversion energy exposure dose is taken to be thecombination of all the pattern conversion steps, again provided that thedose is sufficient to convert about 80%, preferably about 95%, morepreferably about 99%, of the precursor material to metal or metal oxide.

EXAMPLES

[0146] The following examples are only representative of the methods andmaterials for use in the apparati, methods, and processes of thisinvention, and are not to be construed as limiting the scope of theinvention in any way.

Examples 1-6 Determining the Relationship Between Exposure Doses andPrecursor Conversion or Film Thickness of a Deposited Zirconia Layer ona Substrate According to the Invention.

[0147] For Examples 1-3, zirconium precursor material with anacetoacetonate ligand, Zr(AcAc)₄, dissolved in toluene, was spun ontosilicon wafers at about 1250 rpm for about 30 seconds, resulting in aprecursor film of approximately 440 A. The film of Example 1 was formedby thermal conversion on a hot plate at about 180° C. for about 1 hour.The film of Example 2 was formed by photochemical conversion using aKarl Suss MJB-3 mask aligner with a 220 nm cold mirror. Due to the lowintensity output of the mask aligner at DUV (˜0.38 mW/cm²), the exposuretime was about 5 hours (dose where additional exposure does not lead tofurther thickness reduction). The film of Example 3 was formed by takingthe film of Example 1 and further performing thermal conversion at about180° C. for about an additional 1 to 3 hours.

[0148] The thickness and refractive index (see FIG. 8—numerals on curvesrepresent the corresponding Example) of each of the resulting films weremeasured using variable angle spectroscopic ellipsometry (VASE). Theseresults demonstrate that there are significant differences in therefractive index properties for each of the samples which are directlyrelated to the chemical composition of the precursor and to the methodby which it was prepared. The thicknesses were as follows: initialprecursor film ˜440Å Example 1 photoconverted film ˜330Å Example 2thermally converted film ˜360Å Example 3 film having extended thermalconversion ˜320Å

[0149] For Examples 4-6, zirconium precursor material with a 2-ethylhexanoate ligand, Zr(carboxylate)₄, dissolved in hexanes, was spun ontosilicon wafers at about 1500 rpm for about 30 seconds, resulting in aprecursor film of approximately 2340 Å. The film of Example 4 was formedby thermal conversion of the precursor material on a hot plate at about180° C. for about 3 hours. The film of Example 5 was formed byphotochemical conversion of the precursor using a Karl Suss MJB-3 maskaligner with a 220 nm cold mirror. Due to the low photosensitivity ofthis precursor and the low exposure intensity, the exposure time waslengthy, i.e., about 30 hours. The film of Example 6 was formed bytaking the film of Example 4 and further performing thermal conversionat about 180° C. for about an additional 3 hours.

[0150] The thickness and refractive index (see FIG. 8—numerals on curvesrepresent the corresponding Example) of each of the resulting films weremeasured using variable angle spectroscopic ellipsometry (VASE). Theseresults demonstrate that there are significant differences in therefractive index properties for each of the samples which are directlyrelated to the chemical composition of the precursor and to the methodby which it was prepared. The thicknesses were as follows: initialprecursor film ˜2340Å Example 4 photochemically converted film ˜1490ÅExample 5 thermally converted film ˜1140Å Example 6 film having extendedthermal conversion  ˜980Å

Examples 7-9 Effect of the Type of Conversion on the Properties ofBarium Strontium Titanate Layers on a Substrate

[0151] Example 7 demonstrates how thermal treatment may be used toconvert a precursor film to an amorphous film of desired material. ForExamples 7-9, a series of bare silicon wafers was spin-coated with asolution of precursor designed to form BST upon conversion. The waferswere subjected to at least a partial conversion step, which in the caseof Example 7 involved heating at about 160° C. for a total time of about120 minutes in intervals of about 10 minutes. After each conversioninterval, the precursor pattern was developed by rinsing withisopropanol to remove the unconverted precursor. This allowed for adetermination of the time required to thermally print the film, i.e., tohave a substantial amount of film remaining after development withisopropanol. As shown in FIG. 9, this time was determined to beapproximately 20 minutes for thermal conversion.

[0152] Example 8 involved a similar experiment conducted bysubstituting, for thermal conversion, photochemical conversion; theseresults are shown in FIG. 10. This figure demonstrates that the timerequired to photochemically print the film was in the range of about 30minutes to about 60 minutes.

[0153] In Example 9, designed to combine thermal partial conversion or30 pretreatment with photochemical conversion, wafers were subjected toa thermal pretreatment of 160° C. for 10 minutes, then subjected to theabove-described photochemical conversion procedure. The results areshown in FIG. 11.

Examples 10-11 Effect of Layer Composition on the Properties ofElectron-beam Converted Metal-Containing Layers on a Substrate

[0154] Electron-Beam contrast of BST (Example 10) and PZT (Example 11)was performed to determine the photospeed of these materials by exposinga series of fully converted films of each material to increasing dosesof the e-beam and noting, after development, the highest dose at whichthe fraction of film remained at zero and the lowest dose at which thefraction of film remaining reached a value of about 1. The contrast forPZT and BST occurs at about the same range for each, from about 60 toabout 100 μC/cm².

[0155] It is to be understood that the invention is not to be limited tothe exact configuration as illustrated and described herein.Accordingly, all expedient modifications readily attainable by one ofordinary skill in the art from the disclosure set forth herein, or byroutine experimentation therefrom, are deemed to be within the spiritand scope of the invention as defined by the appended claims.

What is claimed is:
 1. A method of converting an organometallicprecursor material to a metal-containing pattern adherent to asubstrate, comprising: applying the organometallic precursor material inan amount sufficient to coat at least a portion of the substrate,wherein said organometallic precursor material is adapted to beconverted to form a metal or metal oxide; pre-converting theorganometallic precursor material by exposing the organometallicprecursor material to a pre-conversion energy exposure dose such thatthe pre-converted precursor material is not converted to a degreesufficient to impair pattern resolution; pattern converting a portion ofthe pre-converted precursor material to convert this portion to apattern-converted material to an extent sufficient to thereby form apattern on the substrate; and developing the portion of thepre-converted precursor material that was not pattern-converted suchthat the pattern remains on the substrate after developing.
 2. Themethod of claim 1, wherein the pattern conversion comprises exposing thepre-converted precursor material to a patterning energy exposure dose,which converts the pre-converted precursor material to metal or metaloxide that adheres to the substrate to an extent sufficient to therebyform a deposited pattern thereon.
 3. The method of claim 2, wherein thepre-conversion energy exposure dose is selected to be about 20% or lessof the combination of the pre-conversion energy exposure dose and thepatterning energy exposure dose, such that the pre-converted precursormaterial is substantially developable.
 4. The method of claim 2, whereinthe pre-conversion energy exposure dose is selected to be from about 20%to about 50% of the combination of the pre-conversion energy exposuredose and the patterning energy exposure dose, such that thepre-converted precursor material is substantially developable.
 5. Themethod of claim 1, wherein the pre-conversion, the pattern-conversion,or both, comprises photochemical metal organic deposition.
 6. The methodof claim 1, wherein the pre-conversion comprises forming a metal ormetal oxide within the organometallic precursor material.
 7. The methodof claim 1, wherein the pre-conversion energy exposure dose is selectedto be from about 30% to about 80% of a maximum pre-conversion energyexposure dose, wherein the maximum pre-conversion energy exposure doseis that energy dose above which the organometallic precursor materialexposed to the pre-conversion energy exposure dose is no longersubstantially developable or above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose adheres tothe substrate to a degree sufficient to impair pattern resolution,wherein the organometallic precursor material exposed to thepre-conversion energy exposure dose is substantially developable.
 8. Themethod of claim 1, wherein the pre-conversion energy exposure dose isselected to be about 50% or more of a maximum pre-conversion energyexposure dose, wherein the maximum pre-conversion energy exposure doseis that energy dose above which the organometallic precursor materialexposed to the pre-conversion energy exposure dose is no longersubstantially developable or above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose adheres tothe substrate to a degree sufficient to impair pattern resolution,wherein the organometallic precursor material exposed to thepre-conversion energy exposure dose is substantially developable.
 9. Themethod of claim 1, wherein the pre-conversion energy exposure dose isselected to be from about 60% to about 99% of a maximum pre-conversionenergy exposure dose, wherein the maximum pre-conversion energy exposuredose is that energy dose above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose is no longersubstantially developable or above which the organometallic precursormaterial exposed to the pre-conversion energy exposure dose adheres tothe substrate to a degree sufficient to impair pattern resolution,wherein the organometallic precursor material exposed to thepre-conversion energy exposure dose is substantially developable.
 10. Asubstrate containing a patterned metal or metal oxide layer formedaccording to the method of claim
 1. 11. The method according to claim 1,wherein the pre-conversion comprises exposing the precursor material toa heat source, and wherein the pattern-conversion comprises exposing thepre-converted precursor material to a light source.
 12. The methodaccording to claim 1, wherein the pre-conversion comprises exposing theprecursor material to a heat source, and wherein the pattern-conversioncomprises exposing the pre-converted precursor material to anelectron-beam source.
 13. The method according to claim 1, wherein thepre-conversion comprises exposing the precursor material to anelectron-beam source, and wherein the pattern-conversion comprisesexposing the pre-converted precursor material to a light source.
 14. Themethod according to claim 1, wherein the pre-conversion comprisesexposing the precursor material to a light source, and wherein thepattern-conversion comprises exposing the pre-converted precursormaterial to a light source.
 15. A method of converting an organometallicprecursor material to a metal-containing pattern adherent to asubstrate, comprising: applying the organometallic precursor material inan amount sufficient to coat at least a portion of the substrate,wherein said organometallic precursor material is adapted to beconverted to form a metal or metal oxide; pre-converting theorganometallic precursor material by exposing the organometallicprecursor material to a pre-conversion energy exposure dose such thatthe pre-converted precursor material is not converted to a degreesufficient to impair pattern resolution; pattern converting a firstportion of the pre-converted precursor material to convert this portionto a pattern-converted material to an extent sufficient to thereby forma first pattern on the substrate; pattern converting a second portion ofthe pre-converted precursor material to convert this portion to apattern-converted material an extent sufficient to thereby form a secondpattern on the substrate; and developing the second portion of thepre-converted precursor material that was pattern-converted such thatthe second pattern remains on the substrate after developing.
 16. Themethod of claim 15, wherein the pattern conversion comprises exposingthe pre-converted precursor material to a patterning energy exposuredose, which converts the pre-converted precursor material to metal ormetal oxide that adheres to the substrate to an extent sufficient tothereby form a deposited pattern thereon.
 17. The method of claim 16,wherein the pre-conversion energy exposure dose is selected to be about20% or less of the combination of the pre-conversion energy exposuredose and the patterning energy exposure dose, such that thepre-converted precursor material is substantially developable.
 18. Themethod of claim 16, wherein the pre-conversion energy exposure dose isselected to be from about 20% to about 50% of the combination of thepre-conversion energy exposure dose and the patterning energy exposuredose, such that the pre-converted precursor material is substantiallydevelopable.
 19. The method of claim 15, wherein the pre-conversion, thepattern-conversion, or both, comprises photochemical metal organicdeposition.
 20. The method of claim 15, wherein the pre-conversioncomprises forming a metal or metal oxide within the organometallicprecursor material.
 21. The method of claim 15, wherein thepre-conversion energy exposure dose is selected to be from about 30% toabout 80% of a maximum pre-conversion energy exposure dose, wherein themaximum pre-conversion energy exposure dose is that energy dose abovewhich the organometallic precursor material exposed to thepre-conversion energy exposure dose is no longer substantiallydevelopable or above which the organometallic precursor material exposedto the pre-conversion energy exposure dose adheres to the substrate to adegree sufficient to impair pattern resolution, wherein theorganometallic precursor material exposed to the pre-conversion energyexposure dose is substantially developable.
 22. The method of claim 15,wherein the pre-conversion energy exposure dose is selected to be about50% or more of a maximum pre-conversion energy exposure dose, whereinthe maximum pre-conversion energy exposure dose is that energy doseabove which the organometallic precursor material exposed to thepre-conversion energy exposure dose is no longer substantiallydevelopable or above which the organometallic precursor material exposedto the pre-conversion energy exposure dose adheres to the substrate to adegree sufficient to impair pattern resolution, wherein theorganometallic precursor material exposed to the pre-conversion energyexposure dose is substantially developable.
 23. The method of claim 15,wherein the pre-conversion energy exposure dose is selected to be fromabout 60% to about 99% of a maximum pre-conversion energy exposure dose,wherein the maximum pre-conversion energy exposure dose is that energydose above which the organometallic precursor material exposed to thepre-conversion energy exposure dose is no longer substantiallydevelopable or above which the organometallic precursor material exposedto the pre-conversion energy exposure dose adheres to the substrate to adegree sufficient to impair pattern resolution, wherein theorganometallic precursor material exposed to the pre-conversion energyexposure dose is substantially developable.
 24. A substrate containing apatterned metal or metal oxide layer formed according to the method ofclaim
 15. 25. The method according to claim 15, wherein thepre-conversion comprises exposing the precursor material to a heatsource, and wherein the pattern-conversion comprises exposing thepre-converted precursor material to a light source.
 26. The methodaccording to claim 15, wherein the pre-conversion comprises exposing theprecursor material to a heat source, and wherein the pattern-conversioncomprises exposing the pre-converted precursor material to anelectron-beam source.
 27. The method according to claim 15, wherein thepre-conversion comprises exposing the precursor material to anelectron-beam source, and wherein the pattern-conversion comprisesexposing the pre-converted precursor material to a light source.
 28. Themethod according to claim 15, wherein the pre-conversion comprisesexposing the precursor material to a light source, and wherein thepattern-conversion comprises exposing the pre-converted precursormaterial to a light source.
 29. An apparatus for converting anorganometallic precursor material to a metal-containing film adherent toa substrate formed by a method according to claim 1, comprising: a loadstation to store the substrate before processing; a means of deliveringthe substrate between processing steps; a pre-convert section, whereinthe substrate is coated, if previously uncoated, with a sufficientamount of the organometallic precursor material and is subjected to afirst converting means in either a series or parallel arrangement; apattern convert section, wherein the organometallic precursor materialcoated on the substrate, subjected to a first converting means, and notcovered by a mask is substantially converted, using a second convertingmeans, to form a metal-containing pattern adherent to the substrate; andan unload station where the pattern-coated substrate is stored afterprocessing.
 30. The apparatus of claim 29, wherein the first and secondconverting means are the same or different, and wherein each comprises aheat source, a light source, a coherent light source, a broadband lightsource, an electron beam source, or an ion beam source.
 31. An apparatusfor converting an organometallic precursor material to ametal-containing film adherent to a substrate formed by a methodaccording to claim 15, comprising: a load station to store the substratebefore processing; a means of delivering the substrate betweenprocessing steps; a pre-convert section, wherein the substrate iscoated, if previously uncoated, with a sufficient amount of theorganometallic precursor material and is subjected to a first convertingmeans in either a series or parallel arrangement; a pattern convertsection, wherein the organometallic precursor material coated on thesubstrate, subjected to a first converting means, and not covered by amask is substantially converted, using a second converting means, toform a metal-containing pattern adherent to the substrate; and an unloadstation where the pattern-coated substrate is stored after processing.32. The apparatus of claim 31, wherein the first and second convertingmeans are the same or different, and wherein each comprises a heatsource, a light source, a coherent light source, a broadband lightsource, an electron beam source, or an ion beam source.
 33. A method ofselecting a pre-conversion energy exposure dose and a patterning energyexposure dose to be used in converting an organometallic precursormaterial to a metal-containing patterned layer comprising at least twopattern elements that are adherent to a substrate, which methodcomprises: determining a relationship between the pre-conversion energyexposure dose in the conversion and the amount of pre-convertedprecursor material that adheres to the substrate; and selecting apre-conversion energy exposure dose that is less than a maximumpre-conversion energy exposure dose, wherein the maximum pre-conversionenergy exposure dose is that energy dose above which the organometallicprecursor material exposed to the pre-conversion energy exposure dose isno longer substantially developable or above which the organometallicprecursor material exposed to the pre-conversion energy exposure doseadheres to the substrate to a degree sufficient to impair patternresolution, such that the patterning energy exposure dose yields anacceptable pattern resolution on the substrate, wherein the acceptablepattern resolution is such that the at least two elements of themetal-containing patterned layer are discrete and not connected by likematerial.
 34. The method of claim 33, further comprising identifying amaximum pre-conversion energy exposure dose based on the dose-conversionrelationship, such that the organometallic precursor material exposed tothe pre-conversion energy exposure dose, but not to the patterningenergy exposure dose is substantially removable during developing. 35.The method of claim 33, wherein the pre-conversion energy exposure doseis selected to be about 20% or less of the combination of thepre-conversion energy exposure dose and the patterning energy exposuredose, such that the pre-converted precursor material is substantiallydevelopable.
 36. The method of claim 33, wherein the pre-conversionenergy exposure dose is selected to be from about 20% to about 50% ofthe combination of the pre-conversion energy exposure dose and thepatterning energy exposure dose, such that the pre-converted precursormaterial is substantially developable.
 37. The method of claim 33,wherein the pre-conversion energy exposure dose is selected to be fromabout 30% to about 80% of a maximum pre-conversion energy exposure dose,wherein the maximum pre-conversion energy exposure dose is that energydose above which the organometallic precursor material exposed to thepre-conversion energy exposure dose is no longer substantiallydevelopable or above which the organometallic precursor material exposedto the pre-conversion energy exposure dose adheres to the substrate to adegree sufficient to impair pattern resolution, wherein theorganometallic precursor material exposed to the pre-conversion energyexposure dose is substantially developable.
 38. The method of claim 33,wherein the pre-conversion energy exposure dose is selected to be about50% or more of a maximum pre-conversion energy exposure dose, whereinthe maximum pre-conversion energy exposure dose is that energy doseabove which the organometallic precursor material exposed to thepre-conversion energy exposure dose is no longer substantiallydevelopable or above which the organometallic precursor material exposedto the pre-conversion energy exposure dose adheres to the substrate to adegree sufficient to impair pattern resolution, wherein theorganometallic precursor material exposed to the pre-conversion energyexposure dose is substantially developable.
 39. The method of claim 33,wherein the pre-conversion energy exposure dose is selected to be fromabout 60% to about 99% of a maximum pre-conversion energy exposure dose,wherein the maximum pre-conversion energy exposure dose is that energydose above which the organometallic precursor material exposed to thepre-conversion energy exposure dose is no longer substantiallydevelopable or above which the organometallic precursor material exposedto the pre-conversion energy exposure dose adheres to the substrate to adegree sufficient to impair pattern resolution, wherein theorganometallic precursor material exposed to the pre-conversion energyexposure dose is substantially developable.